Mixed Sn-Pb halide perovskites are promising absorber materials for solar cells due to the possibility of tuning the bandgap energy down to 1.2-1.3 eV. However, tin-containing perovskites are susceptible to oxidation affecting the optoelectronic properties. In this work, we investigated qualitatively and quantitatively metastable oxygen-induced doping in isolated ASn_xPb_1-xI₃ (where A is methylammonium or a mixture of formamidinium and cesium) perovskite thin films by means of microwave conductivity, structural and optical characterization techniques. We observe that longer oxygen exposure times lead to progressively higher dark conductivities, which slowly decay back to their original levels over days. Here oxygen acts as an electron acceptor, leading to tin oxidation from Sn²⁺ to Sn⁴⁺ and creation of free holes. The metastable oxygen-induced doping is enhanced by exposing the perovskite simultaneously to oxygen and light. Next, we show that doping not only leads to the reduction in the photoconductivity signal but also induces long-term effects even after loss of doping, which is thought to derive from consecutive oxidation reactions leading to the formation of defect states. On prolonged exposure to oxygen and light, optical and structural changes can be observed and related to the formation of SnO_x and loss of iodide near the surface. Our work highlights that even a short-term exposure to oxygen immediately impairs the charge carrier dynamics of the perovskite, while structural perovskite degradation is only noticeable upon long-term exposure and accumulation of oxidation products. Hence, for efficient solar cells, exposure of mixed Sn-Pb perovskites to oxygen during production and operation should be rigorously blocked.

To increase the open-circuit voltage in solar cells based on triple cation, mixed halide perovskites, reducing recombination processes at the interfaces with transport layers (TLs) is key. Here, we investigated the charge carrier dynamics in bilayers and trilayers of Cs_0.05MA_0.10FA_0.85Pb(I_0.97Br_0.03)₃ (CsMAFA) combined with TLs using time-resolved microwave conductance (TRMC) measurements without and with bias illumination (BI). In the bilayers, we find balanced mobilities for electrons and holes in CsMAFA and nearly quantitative carrier extraction. The small, rapidly decaying TRMC signals for n-i-p- and p-i-n triple layers indicate both carriers are extracted. Applying BI leads to the charging of the TLs and the corresponding electric field prevents additional charge extraction, which demonstrates long-lived charge separation over the CsMAFA/TLs. Most importantly, for all bilayer combinations showing long-lived charge separation, an increase of the quasi-Fermi level splitting with respect to that of the CsMAFA layer is found.

Multiple-source thermal evaporation is emerging as an excellent technique to obtain perovskite (PVK) materials for solar cell applications due to its solvent-free processing, accurate control of stoichiometric ratio, and potential for scalability. Nevertheless, the currently reported layer-by-layer deposition approach is afflicted by long processing times caused by the multiple repetitions of thin films, which hinder industrial uptake. On the other hand, the coevaporation entails higher complexity due to the challenges of controlling the sublimation of multiple sources simultaneously. In this work, we propose a simplified approach consisting of a single-cycle deposition (SCD) of three thick precursor layers to obtain high-quality Cs0.15FA0.85PbI2.85Br0.15 (CsFAPbIBr) films. After annealing, the optimized PVK film exhibits comparable properties to the one deposited by multicycle deposition in terms of crystal structure, in-depth uniformity, and optoelectrical properties. Also, the formation and evolution of SCD PVK during annealing are investigated. We found that, in the competitive processes of precursor diffusion and reaction, the presence of cesium bromide can assist precursor mixing driven by the annealing treatment, demonstrating a reaction-limited process in the PVK conversion. With this simplified SCD approach, a PVK film is obtained with expected optical and opto-electronic properties, providing an appealing way for future thermally evaporated PVK device preparation.

State-of-the-art triple cation, mixed halide perovskites are extensively studied in perovskite solar cells, showing very promising performance and stability. However, an in-depth fundamental understanding of how the phase behavior in Cs_0.05FA_0.85MA_0.10Pb(I_0.97Br_0.03)₃ (CsMAFA) affects the optoelectronic properties is still lacking. The refined unit cell parameters a and c in combination with the thermal expansion coefficients derived from X-ray diffraction patterns reveal that CsMAFA undergoes an α–β phase transition at ≈280 K and another transition to the γ-phase at ≈180 K. From the analyses of the electrodeless microwave photoconductivity measurements it is shown that shallow traps only in the γ-phase negatively affect the charge carrier dynamics. Most importantly, CsMAFA exhibits the lowest amount of microstrain in the β-phase at around 240 K, corresponding to the lowest amount of trap density, which translates into the longest charge carrier diffusion length for electrons and holes. Below 200 K a considerable increase in deep trap states is found most likely related to the temperature-induced compressive microstrain leading to a huge imbalance in charge carrier diffusion lengths between electrons and holes. This work provides valuable insight into how temperature-dependent changes in structure affect the charge carrier dynamics in FA-rich perovskites.